WO2019124252A1 - 硬化性樹脂組成物、それを用いた燃料電池およびシール方法 - Google Patents

硬化性樹脂組成物、それを用いた燃料電池およびシール方法 Download PDF

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WO2019124252A1
WO2019124252A1 PCT/JP2018/046113 JP2018046113W WO2019124252A1 WO 2019124252 A1 WO2019124252 A1 WO 2019124252A1 JP 2018046113 W JP2018046113 W JP 2018046113W WO 2019124252 A1 WO2019124252 A1 WO 2019124252A1
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resin composition
curable resin
meth
fuel cell
group
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PCT/JP2018/046113
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English (en)
French (fr)
Japanese (ja)
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哲徳 曽我
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株式会社スリーボンド
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Priority to JP2019561041A priority Critical patent/JPWO2019124252A1/ja
Priority to CN201880081204.9A priority patent/CN111491965A/zh
Priority to KR1020207020098A priority patent/KR20200090918A/ko
Priority to US16/764,963 priority patent/US20200350602A1/en
Priority to EP18891699.3A priority patent/EP3730525A4/en
Publication of WO2019124252A1 publication Critical patent/WO2019124252A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00—Presence of graft polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a curable resin composition.
  • a fuel cell is a power generation device that takes out electricity by chemically reacting hydrogen and oxygen.
  • the fuel cell is a clean next-generation power generator because it has high energy efficiency at the time of power generation and water is produced by the reaction of hydrogen and oxygen.
  • fuel cells There are four types of fuel cells: polymer electrolyte fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells.
  • polymer electrolyte fuel cells have an operating temperature Because of high power generation efficiency with relatively low temperature (around 80 ° C.), it is expected for applications such as automotive power sources, household power generators, small power sources for electronic devices such as mobile phones, emergency power sources, and the like.
  • the cell 1 of the polymer electrolyte fuel cell is an electrolyte membrane electrode assembly 5 (MEA which has a structure in which the polymer electrolyte membrane 4 is sandwiched between the air electrode 3a and the fuel electrode 3b). And a frame 6 for supporting the MEA, and a separator 2 in which a gas flow path is formed.
  • MEA electrolyte membrane electrode assembly 5
  • sealing agents are often used for the purpose of preventing leakage of fuel gas, oxygen gas and the like. Specifically, a sealing agent is used between adjacent separators, between a separator and a frame, between a frame and an electrolyte membrane or MEA, or the like.
  • a polyisobutylene-based polymer As a sealing agent used for a polymer electrolyte fuel cell, a polyisobutylene-based polymer was used because it is a rubber elastic body excellent in gas permeability, low moisture permeability, heat resistance, acid resistance and flexibility.
  • Thermosetting resin composition that undergoes hydrosilylation reaction see Patent Document 1
  • Thermosetting resin composition that undergoes hydrosilylation reaction using a fluoropolyether compound see Patent Document 2
  • hydrosilylation reaction that uses a fluoropolymer A thermosetting resin composition see Patent Document 3
  • a thermosetting resin composition using ethylene-propylene-diene rubber see Patent Document 4
  • JP 2004-111146 A Unexamined-Japanese-Patent No. 2004-175824 Japanese Patent Laid-Open No. 2007-100099 JP 2011-124258 A
  • thermosetting resin compositions of Patent Documents 1 to 4 use a polymer having a large molecular weight in order to improve the sealing property, there is a problem that the viscosity becomes high and the coating workability is lowered.
  • a method of adding a reactive diluent is used to lower the viscosity in the curable resin composition, but when a reactive diluent is added, a curable resin composition such as tensile strength or extensibility, etc.
  • a curable resin composition such as tensile strength or extensibility, etc.
  • the physical properties of a cured product obtained by curing the resin are lowered (see Comparative Examples 2 to 6 described later).
  • This invention is made in view of said condition, and is providing the curable resin composition from which the cured
  • a curable resin composition comprising the following components (A) to (C): (A) having components :( meth) acryloyl groups 1 or more, - [CH 2 C (CH 3) 2] - polymer having a polyisobutylene backbone containing units of component (B): a radical polymerization initiator component (C): A monomer (c1) having an alicyclic structure having a (meth) acryloyl group and a substituent of a hydrocarbon group having a carbon number of 2 to 20 or a monomer having a (meth) acryloyl group and a dicyclopentenyl group or an adamantyl group (c2) ) [2] The curable resin composition according to [1], wherein the component (c1)
  • the component (C) is t-butylcyclohexyl (meth) acrylate, t-butylcyclohexyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate
  • curable resin composition as described in [2].
  • the curable sealant for fuel cells according to [6] which is a curable sealant.
  • the curable sealant for a fuel cell is a sealant between adjacent separators in a fuel cell, or a sealant between a frame of a fuel cell and an electrolyte membrane or an electrolyte membrane electrode assembly.
  • a fuel cell comprising any of the group consisting of: a seal between adjacent separators in a fuel cell, and a seal between a frame of a fuel cell and an electrolyte membrane or an electrolyte membrane electrode assembly, A fuel cell, wherein any seal comprises the cured product of [10].
  • a method of sealing at least a portion between at least two flanges of a sealed part having at least two flanges, wherein at least one flange of the flanges is any of [1] to [5] A step of applying the curable resin composition according to any one of the above items, a step of curing the applied curable resin composition to form a gasket comprising a cured product of the curable resin composition, and the other flange Placing on the gasket, crimping one flange coated with the curable resin composition and the other flange via the gasket, and sealing at least a portion between the at least two flanges;
  • Said sealing method characterized in that it comprises: [15] A method of sealing at least a portion between at least two flanges of a sealed part having at least two flanges, wherein a gasket forming mold is disposed on at least one of the flanges of the flanges.
  • the present invention provides a curable resin composition from which a cured product having high tensile strength and high extensibility can be obtained.
  • the present invention relates to a curable resin composition characterized by containing the following components (A) to (C) and other optional components:
  • Component (A) a polymer having a polyisobutylene skeleton containing — [CH 2 C (CH 3 ) 2 ] — units having one or more (meth) acryloyl groups
  • Component (B) radical polymerization initiator
  • Component (C) a monomer having an alicyclic structure having a (meth) acryloyl group and a substituent of a hydrocarbon group having 2 to 20 carbon atoms (c1) or (meth) acryloyl group and a dicyclopentenyl group or an adamantyl group (C2).
  • the components (A) to (C) of the curable resin composition of the present invention, and other optional components may be used in any combination of those satisfying any of the following conditions.
  • the components (A) to (C) are mutually
  • component (A) used in the present invention (meth) having one or more acryloyl groups, - limited particularly as long as it is a polymer having a polyisobutylene backbone comprising units - [CH 2 C (CH 3 ) 2] It is not a thing.
  • component (A) for example, - [CH 2 C (CH 3 ) 2] - units (polyisobutylene backbone) may if it has a "- [CH 2 C (CH 3 ) 2] - other than the unit Or a polymer containing the
  • the component (A) contains, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more of-[CH 2 C (CH 3 ) 2 ]-units based on the total amount of constituent units. It is appropriate to include.
  • the component (A) contains, for example, 100% by mass or less of-[CH 2 C (CH 3 ) 2 ] -units, 95% by mass or less in another embodiment, and 90% by mass or less in another embodiment. Is appropriate.
  • the component (A) preferably contains 1 to 12, more preferably 2 to 8, still more preferably 2 to 4, and particularly preferably 2 (meth) acryloyl groups.
  • polymer is not limited by theory, it can be defined as, for example, a structure including repeating units of monomers in the main chain of the polymer and refers to a compound consisting of 100 or more repeating units.
  • the (meth) acryloyl group may be present at either the side chain and / or the end of the molecule, but is preferably present at the end of the molecule from the viewpoint of rubber elasticity.
  • the component (A) is preferably a polymer having a polyisobutylene skeleton represented by the following general formula (1) from the viewpoint of obtaining a cured product having high tensile strength and high extensibility.
  • Specific examples of the component (A) include polyisobutylene having a (meth) acryloyloxyalkoxyphenyl group.
  • the main skeleton of the component (A) in the present invention is a polyisobutylene skeleton, but other than mainly using isobutylene as a monomer constituting this polyisobutylene skeleton, it is a range that does not impair the effects of the present invention
  • the monomers of the above may be copolymerized.
  • the component (A) is preferably liquid at normal temperature (25 ° C.) because the coating workability of the curable resin composition is excellent.
  • R 1 represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, preferably a polyvalent aromatic hydrocarbon group, particularly preferably It is a bivalent phenylene group.
  • PIB is the - [CH 2 C (CH 3 ) 2] - comprising units (or - [CH 2 C (CH 3 ) 2] - comprising a unit) showing the polyisobutylene backbone.
  • R 4 represents a C 2 to C 6 divalent hydrocarbon group which may contain an oxygen atom, preferably a C 2 or C 3 divalent hydrocarbon group.
  • R 2 and R 3 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom.
  • R 5 represents a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group.
  • n is an integer of 1 to 6, particularly preferably an integer of 2 to 4.
  • the molecular weight of the component (A) in the present invention is not particularly limited, but in view of fluidity, physical properties after curing, etc., it is preferable that the number average molecular weight by chromatography measurement is, for example, 200 to 500,000. It is preferably 1,000 to 100,000, and particularly preferably 3,000 to 50,000. In addition, the said number average molecular weight was computed by the standard polystyrene conversion method using size permeation chromatography (SEC) unless there is particular notice.
  • SEC size permeation chromatography
  • the viscosity at 25 ° C. of the component (A) in the present invention is not particularly limited, but is, for example, 5 Pa ⁇ s or more, preferably 50 Pa ⁇ s or more, more preferably 100 Pa ⁇ s or more from the viewpoint of workability and the like For example, it is 3000 Pa ⁇ s or less, preferably 2500 Pa ⁇ s or less, more preferably 2000 Pa ⁇ s or less.
  • the particularly preferred viscosity is 1550 Pa ⁇ s.
  • the viscosity was measured using a cone-plate viscometer at 25 ° C.
  • a well-known method can be used. See, for example, Polymer Bulletin, Vol. 6, pages 135-141 (1981), T., et al. P. Liao and J.A. P. Kennedy and Polymer Bulletin, 20, 253-260 (1988), Puskas et al. And the like can be obtained by reacting the terminal hydroxyl group polyisobutylene disclosed in the above with acryloyl chloride or methacryloyl chloride.
  • a method for producing the other component (A) a method obtained by reacting terminal hydroxyl group polyisobutylene with a compound having a (meth) acryloyl group and an isocyanate group, a compound having terminal hydroxyl group polyisobutylene and an isocyanate group A method of reacting a compound having a meth) acryloyl group with a hydroxyl group, or reacting a terminal hydroxyl group polyisobutylene with a (meth) acrylic acid or a (meth) acrylic acid lower ester using a dehydration esterification method or a transesterification method And the like.
  • the method for producing the polyisobutylene represented by the above general formula (1) is not particularly limited, but preferably, the halogen-terminated polyisobutylene disclosed in JP 2013-216782 and the following general formula The method of making it react with the compound which has a (meth) acryloyl group and a phenoxy group which are represented by (2) is mentioned.
  • the halogen-terminated polyisobutylene can be obtained by a known method, for example, by cationic polymerization, and more preferably by living cationic polymerization.
  • R 2 , R 3 , R 4 and R 5 may be as defined in the above formula (1).
  • R 4 represents a divalent hydrocarbon group which may contain an oxygen atom having 2 to 6 carbon atoms.
  • R 2 and R 3 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 5 represents a hydrogen atom, a methyl group or an ethyl group.
  • Examples of the compound represented by the above formula (2) include phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxybutyl (meth) acrylate, phenoxypentyl (meth) acrylate and the like. And preferably phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxybutyl (meth) acrylate, phenoxypentyl (meth) acrylate and the like.
  • the component (B) that can be used in the present invention is a radical polymerization initiator.
  • a photo radical polymerization initiator, organic peroxide (thermal radical polymerization initiator), etc. are mentioned.
  • the curing form of the radical curable resin composition of the present invention can be selected from photocuring, heat curing or redox curing by the selection of the component (B) of the present invention. For example, when it is desired to impart "photo-curable" with respect to a radical curable resin composition, a photo radical polymerization initiator is selected, and when it is desired to impart "curing by heat curing or redox reaction", an organic peroxide is selected. do it.
  • (B) component of this invention is not specifically limited, It is preferable from a viewpoint that surface curability and deep-part curability can be compatible with respect to 100 mass parts of the above-mentioned (A) components preferably. Part, more preferably 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass.
  • the photo radical polymerization initiator which is one of the (B) components which can be used for this invention will not be limited if it is a compound which radical generates by irradiating light (active energy ray).
  • active energy rays are radiations such as alpha rays and beta rays, electromagnetic waves such as gamma rays and X rays, electron rays (EB), ultraviolet rays having a wavelength of about 100 to 400 nm, and visible rays having a wavelength of about 400 to 800 nm. And the like in the broad sense, and is preferably ultraviolet light.
  • Examples of the photoradical polymerization initiator as the component (B) include acetophenone photoradical polymerization initiators, benzoin photoradical polymerization initiators, benzophenone photoradical polymerization initiators, thioxanthone photoradical polymerization initiators, and acyl phosphines.
  • oxide-based radical photopolymerization initiators, titanocene-based radical photopolymerization initiators and the like can be mentioned, and among them, acetophenone-based from the viewpoint that a cured product having excellent surface curability and deep portion curability can be obtained by irradiating active energy rays.
  • the radical photopolymerization initiator and the acyl phosphine oxide radical photopolymerization initiator are preferable. Moreover, these may be used independently and 2 or more types may be used together.
  • acetophenone photoradical polymerization initiators examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2) -Hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1-one Examples thereof include (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer and the like, but not limited thereto.
  • Examples of commercial products of the acetophenone photoradical polymerization initiator include IRGACURE 184, IRGACURE 1173, IRGACURE 2959, IRGACURE 127 (manufactured by BASF), and ESACUREKIP-150 (manufactured by Lamberti s.p.a.).
  • acyl phosphine oxide photo radical polymerization initiator examples include bis (2,4,6-trimethyl benzoyl) -phenyl-phosphine oxide, 2,4,6-trimethyl benzoyl-diphenyl-phosphine oxide and the like. But this is not the case.
  • group radical photopolymerization initiator IRGACURE TPO, IRGACURE819, IRGACURE819DW (made by BASF Corporation) is mentioned.
  • the organic peroxide which is one of the (B) components which can be used for this invention may be a compound which radical species generate
  • the heating is suitably performed, for example, at a temperature of 50 ° C. or more, preferably 80 ° C. or more, more preferably 100 ° C. or more, and in the case of heating, it is also referred to as a thermal radical polymerization initiator.
  • the redox reaction is also referred to as a redox reaction, which is a phenomenon in which a redox species occurs due to radical species released from an organic peroxide.
  • component (B) which brings about a redox reaction for example, by blocking air (oxygen), contact with metal, and appropriate temperature setting (eg, 5 ° C. or higher, preferably room temperature (25 ° C.) ⁇ 5 ° C. or so) Mention may be made of initiators which initiate the reaction.
  • the use of a redox reaction is preferable because radical species can be generated at room temperature.
  • the organic peroxide as component (B) is not particularly limited.
  • methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate Ketone peroxides such as peroxide and acetylacetone peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis Peroxyketals such as (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate and 2,2-bis (t-butylperoxy) butane; t-butyl Hydroperoxide, Kume Hydroperoxides such as hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethyl
  • Peroxides di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2, Dialkyl peroxides such as 5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl peroxide, octa Noyl peroxide, Decanoyl peroxide, La Diacyl peroxides such as uroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, etc .; Peroxy
  • a curing accelerator can be blended for the purpose of accelerating the redox reaction.
  • a curing accelerator is not particularly limited, but preferably, saccharin (o-benzoic sulfide), a hydrazine compound, an amine compound, a mercaptan compound, a transition metal-containing compound, etc. may be used.
  • hydrazine compound examples include 1-acetyl-2-phenylhydrazine, 1-acetyl-2 (p-tolyl) hydrazine, 1-benzoyl-2-phenylhydrazine, 1- (1 ′, 1 ′, 1′- Trifluoro) acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazine, 1-formyl-2-phenylhydrazine, 1-acetyl-2- (p-bromophenyl) hydrazine, 1-acetyl-2- (p And -nitrophenyl) hydrazine, 1-acetyl-2- (2'-phenylethylhydrazine), ethyl carbazate, p-nitrophenylhydrazine, p-trisulfonylhydrazide and the like.
  • amine compound examples include heterocyclic secondary amines such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone, 1,2,3,4-tetrahydroquinaldine, etc .; quinoline, methylquinoline, quinaldine Heterocyclic tertiary amines such as quinoxaline phenazine; aromatic tertiary amines such as N, N-dimethyl-para-toluidine, N, N-dimethyl-anisidine, N, N-dimethylaniline; And azole compounds such as triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, 3-mercaptobenzotrizole and the like.
  • heterocyclic secondary amines such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone,
  • Examples of the mercaptan compounds include n-dodecyl mercaptan, ethyl mercaptan, butyl mercaptan, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), and dipentamer.
  • Examples include erythritol hexakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate and the like.
  • a metal chelate complex salt is used as the transition metal-containing compound.
  • pentadione iron, pentadione cobalt, pentadione copper, propylene diamine copper, ethylene diamine copper, iron naphthate, nickel naphthate, cobalt naphthate, copper naphthate, copper octoate, iron octoate, iron hexoate, iron propionate, acetylacetone vanadium and the like can be mentioned.
  • the curing accelerators described above may be used alone or in combination of two or more.
  • a mixture of saccharin, a hydrazine compound, an amine compound and a transition metal-containing compound is more preferable because it exhibits a good curing promoting effect.
  • the component (C) of the present invention is a monomer (c1) having an alicyclic structure having a (meth) acryloyl group and a substituent of a hydrocarbon group having 2 to 20 carbon atoms, or (meth) acryloyl group and dicyclopentenyl A monomer (c2) having a group or an adamantyl group.
  • the component (C) of the present invention cures rapidly by combination with the other components of the present invention, and provides a curable resin composition in which the cured product has both high tensile strength and high extensibility.
  • the component (C) of the present invention may contain other than a hydrocarbon moiety such as an ether bond.
  • a monomer having a dicyclopentenyl group having a substituent of a hydrocarbon group of 2 to 20 carbon atoms or an adamantyl group having a substituent of a hydrocarbon group of 2 to 20 carbon atoms is used as the component (c1) in the present invention. I will handle it. Hereinafter, a monomer (c1) and a monomer (c2) are demonstrated.
  • the monomer (c1) is a monomer having an alicyclic structure having (i) a (meth) acryloyl group and (ii) a substituent of a hydrocarbon group having 2 to 20 carbon atoms.
  • Examples of the (meth) acryloyl group of the above (i) include an acryloyl group and a methacryloyl group. Among these, a methacryloyl group is preferable because the cured product has high tensile strength and high extensibility.
  • the substituent of the hydrocarbon group having 2 to 20 carbon atoms of (ii) may have, for example, 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms.
  • the hydrocarbon group having 2 to 20 carbon atoms of (ii) does not contain the carbon atom in the alicyclic structure.
  • substituent of the hydrocarbon group having 2 to 20 carbon atoms include, for example, an ethyl group, a propyl group, a butyl group, a t-butyl group, and a pentyl group. More preferably, it is a t-butyl group.
  • examples of the alicyclic structure include cyclohexyl and the like.
  • the monomer (c1) is not particularly limited, and examples thereof include (meth) acrylates having a t-butylcyclohexyl group such as t-butylcyclohexyl (meth) acrylate and t-butylcyclohexyloxyethyl (meth) acrylate. .
  • the monomer (c2) is a monomer having (i) a (meth) acryloyl group and (iii) a dicyclopentenyl group or an adamantyl group. Specific examples and the like of the (meth) acryloyl group of (i) are as described in the above-mentioned monomer (c1).
  • the monomer (c2) is not particularly limited.
  • dicyclopentenyl (meth) acrylate dicyclopentenyl oxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2 -Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like.
  • these may be used independently and 2 or more types may be used together.
  • the compounding amount of the component (C) is preferably 3 to 300 parts by mass, more preferably 5 to 200 parts by mass, and particularly preferably 7 to 100 parts by mass with respect to 100 parts by mass of the component (A). . If the amount of the component (C) is 3 parts by mass or more, there is no fear that the surface curability is lowered, and if it is 300 parts by mass or less, a cured product having a particularly low moisture permeability can be obtained.
  • composition of the present invention (meth) acrylate monomer (not including the component (C) of the present invention), an oligomer having a (meth) acryloyl group (the (A of the present invention) Not including components), various elastomers such as styrenic copolymers, fillers, storage stabilizers, antioxidants, light stabilizers, adhesion promoters, plasticizers, pigments, flame retardants, surfactants, etc. Additives can be used.
  • the present invention may further contain a (meth) acrylate monomer (not including the component (C) of the present invention).
  • the (meth) acrylate monomer is a compound which is polymerized by the radical species generated by the component (B) of the present invention, and is used as a reactive diluent.
  • the component (C) of the present invention is excluded.
  • the (meth) acrylate monomer for example, monofunctional, difunctional, trifunctional and polyfunctional monomers and the like can be used, and among these, it is possible to be compatible with the component (A) of the present invention From the viewpoint of excellent curability, (meth) acrylate monomers having an alkyl group having 5 to 30 carbon atoms are preferable.
  • the (meth) acrylate monomer having an alkyl group having 5 to 30 carbon atoms is not particularly limited, and examples thereof include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate and decyl (meth) ) Acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, n-octadecyl (meth) acrylate, isooctadecyl (meth) acrylate, nonadecane (meth) acrylate, 3-heptyldecyl-1- ( Meta) acrylate, stearyl (meth) acrylate, etc.
  • the (meth) acrylate monomer having an alkyl group having 5 to 30 carbon atoms may have 7 to 25 carbon atoms, or 8 to 20 carbon atoms, and the alkyl group may be an alicyclic group.
  • the (meth) acrylate monomer having a C 5-30 alicyclic group excluding the component (C) of the present invention
  • cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate and the like can be mentioned, and (meth) acrylate monomers can be used alone or as a mixture of two or more.
  • the amount of the (meth) acrylate monomer is preferably 3 to 300 parts by mass, more preferably 5 to 200 parts by mass, and particularly preferably 10 to 100 parts by mass, per 100 parts by mass of the component (A). is there.
  • the oligomer having a (meth) acryloyl group (not including the component (A) of the present invention) is not particularly limited, but, for example, urethane (meth) acrylate of polybutadiene skeleton, urethane (meth) acrylate of hydrogenated polybutadiene skeleton , Urethane (meth) acrylate of polycarbonate skeleton, urethane (meth) acrylate of polyether skeleton, urethane (meth) acrylate of polyester skeleton, urethane (meth) acrylate of castor oil skeleton, isoprene type (meth) acrylate, hydrogenated isoprene type ( Examples thereof include meta) acrylates, epoxy (meth) acrylates, (meth) acrylic group-containing acrylic polymers, etc., among which the excellent compatibility with the component (A) of the present invention and the (meth) acrylate monomer of the above optional components , Po Urethane
  • oligomer refers to a compound comprising 2 to 100 repeating units in a structure with a repeating unit of a monomer in the main chain. Moreover, these may be used independently and 2 or more types may be used together.
  • a styrene copolymer may be blended in order to adjust the rubber physical properties of the cured product.
  • the styrene-based copolymer is not particularly limited.
  • styrene-butadiene copolymer styrene-isoprene copolymer (SIP), styrene-butadiene copolymer (SB), styrene-ethylene-butylene-styrene copolymer
  • SEBS coalesced
  • SIBS styrene-isobutylene-styrene copolymer
  • AS acrylonitrile-styrene copolymer
  • ABS styrene-butadiene-acrylonitrile copolymer
  • a filler may be added to such an extent that storage stability is not impaired for the purpose of improving the modulus of elasticity, fluidity and the like of the cured product.
  • organic powder, inorganic powder, metallic powder and the like can be mentioned.
  • the inorganic powder filler include glass, fumed silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dried clay mineral, dried diatomaceous earth and the like.
  • the compounding amount of the inorganic powder is preferably about 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A). If it is 0.1 parts by mass or more, sufficient effects can be expected, and if it is 100 parts by mass or less, it is preferable because the fluidity of the curable resin composition is not affected and the workability is not deteriorated.
  • Fumed silica can be blended for the purpose of adjusting the viscosity of the curable resin composition or improving the mechanical strength of the cured product.
  • those subjected to a hydrophobization treatment with organochlorosilanes, polyorganosiloxanes, hexamethyldisilazane or the like can be used.
  • Specific examples of fumed silica include commercial products such as Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, R202 and the like manufactured by Nippon Aerosil Co., Ltd. .
  • the filler of the organic powder examples include polyethylene, polypropylene, nylon, crosslinked acrylic, crosslinked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral and polycarbonate.
  • the blending amount of the organic powder is preferably about 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A). If it is 0.1 parts by mass or more, sufficient effects can be expected, and if it is 100 parts by mass or less, it is preferable because the fluidity of the photocurable resin composition is not affected and the workability is not deteriorated. .
  • a storage stabilizer may be added to the present invention.
  • radical absorbers such as benzoquinone, hydroquinone and hydroquinone monomethyl ether
  • metal chelating agents such as ethylenediaminetetraacetic acid or its 2-sodium salt, oxalic acid, acetylacetone, o-aminophenol etc. may also be added. it can.
  • An antioxidant may be added to the present invention.
  • the antioxidant include ⁇ -naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p Quinone compounds such as -benzoquinone, 2,5-diphenyl-p-benzoquinone and 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis (4-methyl-6-tert- Butylphenol), catechol, tert-butyl catechol, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6- (3-tert-butyl-2-) Hydroxy-5-methylbenzyl) -4-methyl He
  • a light stabilizer may be added to the present invention.
  • the light stabilizer for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyl Oxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malone Decanedio
  • An adhesion promoter may be added to the present invention.
  • the adhesion promoter 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , Methacryloxyoctyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, ⁇ -chloropropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl ) Ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyl
  • hydroxyethyl methacrylate phosphate, methacryloxy oxyethyl acid phosphate, methacryloxy oxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl methacrylate phosphate and the like are preferable.
  • the content of the adhesion promoter is preferably 0.05 to 30 parts by mass, and more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the component (A).
  • plasticizers include petroleum-based process oils such as muffin-based process oils, naphthene-based process oils, and aromatic-based process oils, and acrylic acid plasticizers and dibasic acids such as diethyl phthalate, dioctyl phthalate and dibutyl adipate. Examples thereof include low molecular weight liquid polymers such as dialkyl, liquid polybutene and liquid polyisoprene.
  • the flame retardant include hydrated metal compounds, phosphorus, silicones and nitrogen compounds.
  • surfactant an anionic surfactant, a nonionic surfactant, a nonionic surfactant etc. are mentioned, for example. These may be used alone or in combination of two or more.
  • the curable resin composition of the present invention can be produced by a conventionally known method. For example, by blending predetermined amounts of the components (A) to (C) and other optional components, mixing is preferably performed at a temperature of 10 to 70 ° C., preferably 0.1 to 5 using a mixing means such as a mixer. It can be manufactured by time mixing. Moreover, it is preferable to manufacture in a light-shielding environment.
  • ⁇ Coating method> As a method of apply
  • the curable resin composition of the present invention is preferably liquid at 25 ° C. from the viewpoint of coatability.
  • the curable resin composition of the present invention can adopt various curing methods corresponding to the type of radical polymerization initiator. Specifically, when the radical polymerization initiator is a photo radical polymerization initiator, heating (or activation air) is performed when the radical polymerization initiator is an organic peroxide by irradiating light (active energy ray). The blocking reaction and the contact with the metal ions initiate the curing reaction.
  • the light source for curing the curable resin composition of the present invention by irradiation with light (active energy ray) such as ultraviolet light and visible light is not particularly limited.
  • low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, super A high pressure mercury lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED, a fluorescent lamp, sunlight, an electron beam irradiation apparatus and the like can be mentioned.
  • the irradiation dose of light irradiation is preferably 10 kJ / m 2 or more, more preferably 15 kJ / m 2 or more, from the viewpoint of the properties of the cured product.
  • the heating temperature is, for example, 50 ° C. or more, preferably 80 ° C. or more, more preferably 100 ° C. or more.
  • the cured product of the present invention irradiates light (active energy ray) to the curable resin composition of the present invention according to the above curing method, blocks air, contacts with metal ions, and heats it. It is made to harden by.
  • the cured product of the present invention is not limited as long as the curable resin composition of the present invention is cured.
  • the curable resin composition of the present invention or the cured product thereof is a curable sealing agent.
  • the sealing agent includes applications such as an adhesive, a coating agent, a casting agent, a potting agent and the like.
  • the curable resin composition of this invention is a liquid at 25 degreeC.
  • the curable resin composition of the present invention or the cured product thereof is a rubber elastic body excellent in low gas permeability, low moisture permeability, heat resistance, acid resistance and flexibility.
  • the curable resin composition of the present invention or the cured product thereof is a rubber elastic body excellent in low gas permeability, low moisture permeability, heat resistance, acid resistance and flexibility.
  • fuel cells solar cells, dye-sensitized solar cells, lithium ion batteries, electrolytic capacitors, liquid crystal displays, organic EL displays, electronic paper, LEDs, hard disk drives, photodiodes, optical communication circuits, electric cables, cables, optical fibers , Optical isolators, laminates such as IC cards, sensors, substrates, medical / medical instruments / devices, etc.
  • the curable resin composition of the present invention is rapidly cured by heating, irradiation of active energy rays such as ultraviolet rays, etc., and the cured product is excellent in high tensile strength and high extensibility. Is particularly preferred.
  • a fuel cell is a power generation device that takes out electricity by chemically reacting hydrogen and oxygen.
  • fuel cells There are four types of fuel cells: polymer electrolyte fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells.
  • polymer electrolyte fuel cells are Since the operating temperature is relatively low (around 80 ° C.) and high power generation efficiency, it is used for applications such as automotive power sources, household power generators, small power sources for electronic devices such as mobile phones, emergency power sources, and the like.
  • an electrolyte membrane electrode assembly having a structure in which a polymer electrolyte membrane 4 is sandwiched between an air electrode 3a and a fuel electrode 3b is the cell 1 of a typical solid polymer fuel cell. 5 (MEA), a frame 6 for supporting the MEA, and a separator 2 in which a gas flow path is formed.
  • fuel gas hydrogen gas
  • oxidizing gas oxygen gas
  • the solid polymer fuel cell is started, fuel gas (hydrogen gas) and oxidizing gas (oxygen gas) are supplied through the oxidizing gas flow path 8a and the fuel gas flow path 8b. Further, it flows through the flow path 9 of the cooling water for the purpose of alleviating the heat generation at the time of power generation.
  • a stack of several hundreds of these cells in a package is called a cell stack 10 as shown in FIG.
  • a sealing agent is often used for the purpose of preventing leakage of fuel gas, oxygen gas, and the like. Specifically, a sealing agent is used between adjacent separators, between a separator and a frame, between a frame and an electrolyte membrane or MEA, or the like.
  • polymer electrolyte membrane examples include a cation exchange membrane having ion conductivity, preferably a fluorine-based polymer having a sulfonic acid group because it is preferably chemically stable and resistant to operation at high temperatures.
  • a cation exchange membrane having ion conductivity preferably a fluorine-based polymer having a sulfonic acid group because it is preferably chemically stable and resistant to operation at high temperatures.
  • commercially available products include Nafion (registered trademark) manufactured by DuPont, Flemion (registered trademark) manufactured by AGC Corporation (formerly Asahi Glass Co., Ltd.), Aciplex (registered trademark) manufactured by Asahi Kasei Corporation, and the like.
  • the polymer electrolyte membrane is a difficultly adhering material, but it can be adhered by using the curable resin composition of the present invention.
  • the fuel electrode is called a hydrogen electrode or an anode, and known fuel electrodes are used.
  • carbon supported on a catalyst such as platinum, nickel or ruthenium is used.
  • the air electrode is called an oxygen electrode or a cathode, and a known one is used.
  • carbon supported on a catalyst such as platinum or alloy is used.
  • the surface of each electrode may be provided with a gas diffusion layer that works to diffuse the gas and keep the electrolyte moist.
  • the gas diffusion layer known ones are used, and examples thereof include carbon paper, carbon cloth, carbon fiber and the like.
  • the separator 2 has fine uneven channels, through which a fuel gas and an oxidizing gas are supplied and supplied to the electrode.
  • the separator is made of aluminum, stainless steel, titanium, graphite, carbon or the like.
  • the frame supports and reinforces the thin film electrolyte membrane or MEA so as not to break it.
  • the material of the frame include thermoplastic resins such as polyvinyl chloride, polyethylene naphthalate, polyethylene terephthalate, polypropylene and polycarbonate.
  • thermoplastic resins such as polyvinyl chloride, polyethylene naphthalate, polyethylene terephthalate, polypropylene and polycarbonate.
  • a radical photopolymerization initiator as (B) component, in order to bond a member together using the curable resin composition of this invention, or its hardened
  • the fuel cell of the present invention is a fuel cell characterized by being sealed by the curable resin composition of the present invention or a cured product thereof.
  • a separator, a frame, an electrolyte, a fuel electrode, an air electrode, MEA, etc. are mentioned. More specific sealing points include between adjacent separators, between a separator and a frame, between a frame and an electrolyte membrane or MEA, and the like.
  • the main purpose of the seal of “between the separator and the frame” or “between the polymer electrolyte membrane or MEA and the frame” is to prevent gas mixing and leakage, and between the adjacent separators.
  • the purpose of the seal is to prevent gas leakage and to prevent the coolant from leaking out of the coolant channel.
  • acid resistance is calculated
  • the sealing method using the curable resin composition of the present invention is not particularly limited, but typically, FIPG (form in place gasket), CIPG (cure in place gasket), MIPG (mold in place gasket), Liquid injection molding etc. are mentioned.
  • the curable resin composition of the present invention is applied to a flange of a sealed part by an automatic coating device or the like, and the curable resin composition is cured and adhesively sealed in a state of being bonded to the other flange. It is a method. More specifically, a method of sealing at least a portion between at least two flanges of a sealed part having at least two flanges, wherein the curable resin composition as described above is applied to at least one surface of the flanges. Applying a coating, bonding the one flange coated with the curable resin composition and the other flange through the curable resin composition, curing the curable resin composition, Sealing at least a portion between the at least two flanges.
  • the flanges are capable of transmitting light of active energy rays, and the flange capable of transmitting active energy rays such as ultraviolet light as described above. It is preferable that the curable resin composition be cured by irradiation from the side.
  • the curable resin composition of the present invention is bead-coated on a flange of a part to be sealed by an automatic coating device or the like, and the curable resin composition is cured to form a gasket. And, it is a method of pasting together with the other flange and performing compression seal.
  • a method of sealing at least a portion between at least two flanges of a sealed part having at least two flanges wherein the curable resin composition described above is applied to at least one of the flanges Applying the coating, curing the curable resin composition, and forming a gasket comprising the cured product of the curable resin composition, placing the other flange on the gasket, and curing the curable resin composition And pressure-bonding the one flange coated with the other flange with the other flange through the gasket, and sealing at least a part between the at least two flanges.
  • a radical photopolymerization initiator it is preferable to cure the curable resin composition by irradiating the applied curable resin composition with an active energy ray such as ultraviolet light.
  • a mold is previously pressed against the flange of the part to be sealed, the curable resin composition is injected into the cavity formed between the mold and the flange, and the curable resin composition is cured to form a gasket. And, it is a method of pasting together with the other flange and performing compression seal.
  • die is a material which can be light-transmitted, and, specifically, glass, polymethyl methacrylate (PMMA), a polycarbonate, a cycloolefin polymer, an olefin etc. are mentioned.
  • a fluorine-based or silicone-based mold release agent to the mold in advance. More specifically, a method of sealing at least a portion between at least two flanges of a sealed part having at least two flanges, wherein a gasket forming mold is formed on at least one of the flanges Placing the curable resin composition into at least a part of the space between the gasket forming mold and the flange on which the mold is placed; curing the curable resin composition; Forming a gasket comprising a cured product of the curable resin composition, removing the mold from the one flange, and arranging the other flange on the gasket to form the one flange and the other flange.
  • a sealing method characterized.
  • a radical photopolymerization initiator used as the component (B)
  • MIPG press-bonds the mold to the flange of the part to be sealed in advance, and cures in the cavity created between the mold and the flange of the material that can transmit light. It is preferable to inject the organic resin composition and irradiate an active energy ray such as ultraviolet rays to photocure to form a gasket.
  • the curable resin composition of the present invention is poured into a mold by a specific pressure and cured to form a gasket. And, it is a method of pasting together with the other flange and performing compression seal.
  • die is a material which can be light-transmitted, and, specifically, glass, PMMA, a polycarbonate, a cycloolefin polymer, an olefin etc. are mentioned.
  • a fluorine-based or silicone-based mold release agent to the mold in advance.
  • the mold is preferably made of a light transmittable material, and the curable resin composition which has been poured by irradiating active energy rays such as ultraviolet rays is photocured To form a gasket.
  • the a1 contains-[CH 2 C (CH 3 ) 2 ]-units and contains 2 acryloyl groups. More specifically, in the general formula (1), a 1 represents a phenylene group, PI 1 represents a polyisobutylene skeleton, R 4 represents a hydrocarbon group having 2 carbon atoms, and R 2 and R 3 Each independently represents a hydrogen atom, and R 5 is a hydrogen atom. More specifically, it is a polymer represented by the general formula (3). In addition, the number average molecular weight (the chromatography method, polystyrene conversion) of a1 component was 11,100, and the viscosity (25 degreeC) of a1 component was 1550 Pa.s.
  • test methods used in the examples and comparative examples in Table 1 are as follows.
  • the thickness of a curable resin composition is set to 1 mm, and ultraviolet rays of 45 kJ / m 2 of integrated light quantity are irradiated to cure, thereby producing a sheet-like cured product.
  • the pressing surface of A-type durometer (hardness meter) parallel to the test piece the sheet-like cured product is stacked 6 sheets and set to a thickness of 6 mm
  • press with a force of 10 N Adhere the pressure surface to the sample.
  • the hardness is preferably 25 or more, and more preferably 30 or more.
  • the thickness of the curable resin composition is set to 1 mm, and ultraviolet rays of 45 kJ / m 2 of integrated light quantity are irradiated to cure, thereby producing a sheet-like cured product.
  • Make a test piece by punching with No. 3 dumbbell, and mark the test piece with 20 mm intervals. It is fixed to the chuck in the same manner as the tensile strength measurement, and pulled at a tensile speed of 500 mm / min until the specimen is cut. During the measurement, the distance between the marked lines is measured with a caliper until the test piece is cut because the test piece extends and the distance between the marked lines increases.
  • the rate of elongation be “elongation (%)”. Evaluation is made based on the following criteria, and the results are shown in Table 1. From the viewpoint of high extensibility, the elongation rate is preferably 130% or more, and more preferably 200% or more.
  • the thickness of a curable resin composition is set to 1 mm, and ultraviolet rays of 45 kJ / m 2 of integrated light quantity are irradiated to cure, thereby producing a sheet-like cured product.
  • the test piece is pulled at a pulling speed of 50 mm / min to measure the maximum load. Let strength at the time of the maximum load be "tensile strength (MPa)".
  • the tensile strength is preferably 1.2 MPa or more, more preferably 2.0 MPa or more.
  • the present invention can provide a curable resin composition capable of obtaining a cured product having high tensile strength and high elongation (elongation rate) and having sufficient hardness. Recognize.
  • comparative example 1 of Table 1 is a composition which does not contain the (C) component of this invention, it turns out that hardness and tensile strength are inferior.
  • Comparative Examples 2 to 6 are compositions using a reactive diluent instead of the component (C) of the present invention, but it is understood that the composition is inferior in any of hardness, tensile strength and extensibility.
  • Viscosity measurement method The viscosity (Pa ⁇ s) of the curable resin composition of Examples 2, 5, 7, 8 and 9 was measured by a cone plate type viscometer (manufactured by Brookfield Co., Ltd.) based on the following measurement conditions did. The measured values of viscosity are as shown in Table 1.
  • Example 2 was 26 Pa ⁇ s
  • Example 5 was 45 Pa ⁇ s
  • Example 7 was 50 Pa ⁇ s
  • Example 8 was 18 Pa ⁇ s
  • Example 9 was 48 Pa ⁇ s, so application with a screen printing machine etc. It was confirmed that the viscosity was as low as possible.
  • the viscosity is preferably 200 Pas or less, particularly preferably 100 Pa ⁇ s or less.
  • the moisture permeability (g / m 2 ⁇ 24 hours (h)) was calculated and evaluated based on the following evaluation criteria. The results are shown in Table 2.
  • the detailed test method conforms to JIS Z 0208.
  • the moisture permeability is preferably less than 50 g / m 2 ⁇ 24 h when used as a curable sealant for fuel cells.
  • Moisture permeability is less than 10 g / m 2 ⁇ 24 h: Moisture permeability is 10 g / m 2 ⁇ 24 h or more, 50 g / m 2 ⁇ 24 h Less: Moisture permeability is 50 g / m 2 ⁇ 24 h or more
  • the hydrogen gas barrier property is preferably less than 1 ⁇ 10 ⁇ 15 mol ⁇ m / m 2 ⁇ s ⁇ Pa when used as a photocurable sealing agent for fuel cells.
  • Good Less than 1 ⁇ 10 -15 mol ⁇ m / m 2 ⁇ s ⁇ Pa
  • Defect 1 ⁇ 10 -15 mol ⁇ m / m 2 ⁇ s ⁇ Pa or more
  • the present invention is a curable resin composition capable of obtaining a cured product having high tensile strength and high extensibility, and can be used for various sealing applications.
  • a curable sealing agent for fuel cells since it is effective as a curable sealing agent for fuel cells, it is industrially useful.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Organic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
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  • Sealing Material Composition (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Fuel Cell (AREA)
PCT/JP2018/046113 2017-12-18 2018-12-14 硬化性樹脂組成物、それを用いた燃料電池およびシール方法 WO2019124252A1 (ja)

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CN201880081204.9A CN111491965A (zh) 2017-12-18 2018-12-14 固化性树脂组合物、使用其的燃料电池和密封方法
KR1020207020098A KR20200090918A (ko) 2017-12-18 2018-12-14 경화성 수지 조성물, 이를 이용한 연료 전지 및 실링 방법
US16/764,963 US20200350602A1 (en) 2017-12-18 2018-12-14 Curable resin composition, fuel cell using same, and sealing method using same
EP18891699.3A EP3730525A4 (en) 2017-12-18 2018-12-14 COMPOSITION OF HARDENABLE RESIN, FUEL CELL, AND SEALING PROCESS USING IT

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6956840B1 (ja) * 2020-09-30 2021-11-02 住友理工株式会社 燃料電池用部材およびその製造方法
WO2023002973A1 (ja) * 2021-07-21 2023-01-26 株式会社スリーボンド 光硬化性組成物
CN115885122A (zh) * 2020-08-31 2023-03-31 三键有限公司 固化性树脂组合物、燃料电池以及密封方法
WO2023090088A1 (ja) * 2021-11-18 2023-05-25 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11787931B2 (en) * 2018-11-21 2023-10-17 Threebond Co., Ltd. Photocurable resin composition, sealing material for fuel cell, cured product thereof, fuel cell, and sealing method
CN114316809B (zh) * 2022-01-10 2023-10-20 南亚新材料科技股份有限公司 锂电池用密封胶及其制备方法
CN114149678B (zh) * 2022-01-10 2023-10-10 南亚新材料科技股份有限公司 热固性树脂组合物、增强材料、覆金属层压板及其应用
CN114665151B (zh) * 2022-04-14 2024-05-31 北京卫蓝新能源科技有限公司 一种聚合物电解质、其制备方法及在固态电池中的应用

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08169922A (ja) * 1994-09-02 1996-07-02 Roehm Gmbh 櫛形ポリマー
JP2004075824A (ja) 2002-08-15 2004-03-11 Shin Etsu Chem Co Ltd 硬化性フルオロポリエーテル系ゴム組成物及びゴム製品
JP2004111146A (ja) 2002-09-17 2004-04-08 Mitsui Chemicals Inc 燃料電池シール部品用重合体組成物、燃料電池シール部品、燃料電池シール部品の製造方法、および燃料電池
JP2007100099A (ja) 2002-12-05 2007-04-19 Daikin Ind Ltd 含フッ素ポリマー組成物及び硬化体
JP2010528407A (ja) * 2007-05-18 2010-08-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 弾性積層接着剤によって保護された有機電子デバイス
JP2011124258A (ja) 2009-12-08 2011-06-23 Furukawa Electric Co Ltd:The 窒化物系ダイオード
JP2013216782A (ja) 2012-04-09 2013-10-24 Kaneka Corp 硬化性組成物およびその用途
JP2014517857A (ja) * 2011-04-27 2014-07-24 ヘンケル・ユーエス・アイピー・リミテッド・ライアビリティ・カンパニー 低温シーリング機能を備える硬化性エラストマー組成物
WO2016152392A1 (ja) * 2015-03-24 2016-09-29 セメダイン株式会社 硬化性組成物
WO2017018546A1 (ja) * 2015-07-30 2017-02-02 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法
WO2017018547A1 (ja) * 2015-07-30 2017-02-02 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法
WO2017029978A1 (ja) * 2015-08-18 2017-02-23 株式会社スリーボンド 燃料電池用光硬化性シール剤、燃料電池およびシール方法
WO2017038340A1 (ja) * 2015-09-02 2017-03-09 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法
WO2018047479A1 (ja) * 2016-09-06 2018-03-15 株式会社スリーボンド 硬化性樹脂組成物、それを用いた燃料電池およびシール方法
WO2018190415A1 (ja) * 2017-04-14 2018-10-18 株式会社スリーボンド 光硬化性樹脂組成物、それを用いた燃料電池およびシール方法

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08169922A (ja) * 1994-09-02 1996-07-02 Roehm Gmbh 櫛形ポリマー
JP2004075824A (ja) 2002-08-15 2004-03-11 Shin Etsu Chem Co Ltd 硬化性フルオロポリエーテル系ゴム組成物及びゴム製品
JP2004111146A (ja) 2002-09-17 2004-04-08 Mitsui Chemicals Inc 燃料電池シール部品用重合体組成物、燃料電池シール部品、燃料電池シール部品の製造方法、および燃料電池
JP2007100099A (ja) 2002-12-05 2007-04-19 Daikin Ind Ltd 含フッ素ポリマー組成物及び硬化体
JP2010528407A (ja) * 2007-05-18 2010-08-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 弾性積層接着剤によって保護された有機電子デバイス
JP2011124258A (ja) 2009-12-08 2011-06-23 Furukawa Electric Co Ltd:The 窒化物系ダイオード
JP2014517857A (ja) * 2011-04-27 2014-07-24 ヘンケル・ユーエス・アイピー・リミテッド・ライアビリティ・カンパニー 低温シーリング機能を備える硬化性エラストマー組成物
JP2013216782A (ja) 2012-04-09 2013-10-24 Kaneka Corp 硬化性組成物およびその用途
WO2016152392A1 (ja) * 2015-03-24 2016-09-29 セメダイン株式会社 硬化性組成物
WO2017018546A1 (ja) * 2015-07-30 2017-02-02 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法
WO2017018547A1 (ja) * 2015-07-30 2017-02-02 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法
WO2017029978A1 (ja) * 2015-08-18 2017-02-23 株式会社スリーボンド 燃料電池用光硬化性シール剤、燃料電池およびシール方法
WO2017038340A1 (ja) * 2015-09-02 2017-03-09 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法
WO2018047479A1 (ja) * 2016-09-06 2018-03-15 株式会社スリーボンド 硬化性樹脂組成物、それを用いた燃料電池およびシール方法
WO2018190415A1 (ja) * 2017-04-14 2018-10-18 株式会社スリーボンド 光硬化性樹脂組成物、それを用いた燃料電池およびシール方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
POLYMER BULLETIN, vol. 6, 1981, pages 135 - 141
See also references of EP3730525A4
T. P. LIAO, J. P. KENNEDY AND POLYER BULLETIN, vol. 20, 1988, pages 253 - 260

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115885122A (zh) * 2020-08-31 2023-03-31 三键有限公司 固化性树脂组合物、燃料电池以及密封方法
JP6956840B1 (ja) * 2020-09-30 2021-11-02 住友理工株式会社 燃料電池用部材およびその製造方法
WO2022070486A1 (ja) * 2020-09-30 2022-04-07 住友理工株式会社 燃料電池用部材およびその製造方法
JP2022057075A (ja) * 2020-09-30 2022-04-11 住友理工株式会社 燃料電池用部材およびその製造方法
WO2023002973A1 (ja) * 2021-07-21 2023-01-26 株式会社スリーボンド 光硬化性組成物
WO2023090088A1 (ja) * 2021-11-18 2023-05-25 株式会社スリーボンド 光硬化性樹脂組成物、燃料電池およびシール方法

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